CN107353013A - 一种致密高抗氧化性氮化锆‑赛隆复合陶瓷的制备方法 - Google Patents

一种致密高抗氧化性氮化锆‑赛隆复合陶瓷的制备方法 Download PDF

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CN107353013A
CN107353013A CN201710726448.5A CN201710726448A CN107353013A CN 107353013 A CN107353013 A CN 107353013A CN 201710726448 A CN201710726448 A CN 201710726448A CN 107353013 A CN107353013 A CN 107353013A
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zirconium nitride
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马北越
任鑫明
苏畅
尹月
于景坤
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Northeastern University China
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Abstract

本发明公开了一种致密高抗氧化性氮化锆‑赛隆复合陶瓷的制备方法。通过原位引入氮化锆增强相，提高赛隆的强度，改善其致密度和抗氧化性。大致分为两部分，首先采用碳热还原氮化法制备氮化锆‑赛隆复合粉体，进而选用常压烧结制得氮化锆‑赛隆复合陶瓷。工艺流程合理，原料成本低廉，而且所得氮化锆‑赛隆复合陶瓷制品拥有极其出色的致密度和抗氧化性。

Description

一种致密高抗氧化性氮化锆-赛隆复合陶瓷的制备方法
技术领域
本发明属于结构陶瓷及资源与二次资源利用技术领域，特别涉及一种致密高抗氧化性氮化锆-赛隆复合陶瓷的制备方法。
背景技术
氮化锆具有优异的耐磨、耐蚀、抗氧化性、化学稳定性，是原子能、军工、石油化工等领域的重要原料，尤其以出色的高温抗氧化性和高温耐腐蚀性被人所熟知。氮化锆凭借优秀的高温性能主要被用作原子能反应堆保护层、飞机发动机材料、冶金反应容器、复合材料增强相等。
赛隆陶瓷是上世纪末发展起来的Si-Al-O-N四元系高温结构材料，具有优秀的力学、热学性能，是目前炙手可热的高温陶瓷材料。凭借自身的出色性能，赛隆陶瓷被广泛应用在冶金、建材、消防、机械等领域。
历经数十年的发展，赛隆材料从早期的单相材料逐步演化为如今的复合材料。因为对单相材料来说，往往由于内在结构的限制，会在制备和使用上存在一定的缺陷。通过选择性的添加新相，能预设性的改变和提升材料的性能，进而制备出更加优异的新材料，以满足日益增长的材料需求。
因此，复合赛隆陶瓷是赛隆材料未来发展的方向，像引入氧化锆相，可有效改善赛隆材料的断裂韧性；引入碳化硅相能通过细化晶粒提升赛隆材料的强度。工业上生产赛隆材料常采用高纯的硅铝系原料，通过高温反应合成，成本过于昂贵，而且工艺也不够便捷，限制了其大范围推广应用。选用更廉价的原料，优化工艺流程，完善制备体系是赛隆材料面临和急需解决的问题。
发明内容
本发明提供了一种致密高抗氧化性氮化锆-赛隆复合陶瓷的制备方法，该方法通过原位引入氮化锆增强相，提高赛隆的强度，改善其致密度和抗氧化性。
本发明采用的技术方案大致分为两部分，首先采用碳热还原氮化法制备氮化锆-赛隆复合粉体，再选用常压烧结制得氮化锆-赛隆复合陶瓷；具体步骤如下：
(1)将经过破碎处理的粉煤灰、碳粉、锆英石按质量分数20％～50％、20％～50％、10％～30％配料，以无水乙醇做球磨介质，经5～15h充分球磨混匀；
(2)将球磨混匀的配料在10～30MPa下压制成型，接着在70～120℃温度下干燥10～20h。随后将试样放入通有气氛的高温炉，在1300～1600℃保温2～10h合成氮化锆-赛隆复合粉体；
(3)将氮化锆-赛隆复合粉体磨碎，加入3％～5％粘结剂，以无水乙醇做球磨介质，经5～15h充分球磨混匀；
(4)将球磨混匀的配料在100～300MPa下压制成型，接着在70～120℃温度下干燥10～20h。随后将试样放入通有气氛的高温炉，在1400～1600℃保温5～10h得到氮化锆-赛隆复合陶瓷。
所述的粉煤灰、锆英石处理要求为破碎至粒度≤45μm；
所述的碳粉包括活性炭、炭黑、焦炭、煤粉中的一种；
所述(1)和(3)中的球磨设备为行星球磨机，转速设定在300～500r·min-1范围内，单向运行，每运行5h停歇1h；
所述(2)和(4)中的压制方式为模压成型、等静压成型中一种，保压时间为5min；
所述(2)和(4)中的气氛为高纯氮气，流量控制在1～3L·min-1；
所述(2)和(4)中的高温炉为可通气氛的箱式电阻炉、管式电阻炉、隧道窑中的一种。升温速率设定为：以8℃·min-1的速率从室温升温至1000℃，接着以5℃·min-1的速率升温至1000～1300℃，再按3℃·min-1的速率升温至目标温度。
本发明的有益效果是：
(1)原料取自工业固体废弃物和低成本天然矿物，降低了大量的生产成本；
(2)采用两步法，先碳热还原氮化合成氮化锆-赛隆复合粉体，再通过常压固相烧结制得氮化锆-赛隆复合陶瓷。工艺设计合理，设备要求低，适宜推广；
(3)所得氮化锆-赛隆复合陶瓷制品拥有极其出色的致密度和抗氧化性，适合用于冶金耐火材料及其他先进领域高温服役件等。
附图说明
图1是本发明的工艺流程图。
图2是粉煤灰、活性炭、锆英石质量分数为40％、40％、20％时，在1400℃保温4h合成氮化锆-赛隆复合粉体的XRD图谱，由图可知主晶相为ZrN和β-Sialon。
具体实施方式
以下取部分实施例对本发明的技术方案进行清晰完整的描述，显然，以下实施例只是本发明的部分成果。实际操作时可选用其他原料或调整部分技术参数。
为免赘述，先将实施方案所涉及的部分物料参数做统一描述，具体实施例中将不再重复：
以下实施例中粉煤灰(粒度≤75μm)、锆英石(粒度≤45μm)的具体成分为：
以下实施例中球磨设备为行星式球磨机，转速设定为300r·min-1，单向运行，每运行5h停歇1h；
以下实施例中压样方式均为手动模压压制，设备为手动压力机；
以下实施例中粘结剂为聚乙烯醇，添加量为3％；
以下实施例中氮气流量设定为1.5L·min-1；
以下实施例中所选高温炉为可通气氛的管式电阻炉。
实施例1
(1)将经过破碎处理的粉煤灰、锆英石和活性炭按质量分数40％、20％、40％混合，在球磨机内充分球磨10h；
(2)将球磨混匀的配料在20MPa下压制成型，接着在80℃恒温干燥箱保温20h。干燥完成后，将试样放入管式电阻炉，接通电源，打开氮气，在1400℃保温4h合成氮化锆-赛隆复合粉体；
(3)将合成的氮化锆-赛隆复合粉体在研钵磨碎，加入适量酒精，在球磨机内充分球磨10h；
(4)将球磨混匀的氮化锆-赛隆复合粉体在200MPa下压制成型，接着在80℃恒温干燥箱保温20h。干燥完成后，将试样放入管式电阻炉，接通电源，打开氮气，在1500℃保温6h得到氮化锆-赛隆复合陶瓷成品。
对制品氮化锆-赛隆复合陶瓷进行检测获得以下参数：显气孔率3％，常温耐压强度30MPa；900℃恒温氧化6h后，表面有少量气孔，仅有微小增重，抗氧化性良好。
实施例2
(1)将经过破碎处理的粉煤灰、锆英石和活性炭按质量分数35％、30％、35％混合，在球磨机内充分球磨10h；
(2)将球磨混匀的配料在20MPa下压制成型，接着在80℃恒温干燥箱保温20h。干燥完成后，将试样放入管式电阻炉，接通电源，打开氮气，在1500℃保温4h合成氮化锆-赛隆复合粉体；
(3)将合成的氮化锆-赛隆复合粉体在研钵磨碎，加入适量酒精，在球磨机内充分球磨10h；
(4)将球磨混匀的氮化锆-赛隆复合粉体在200MPa下压制成型，接着在80℃恒温干燥箱保温20h。干燥完成后，将试样放入管式电阻炉，接通电源，打开氮气，在1550℃保温6h得到氮化锆-赛隆复合陶瓷成品。
对制品氮化锆-赛隆复合陶瓷进行检测获得以下参数：显气孔率0.2％，常温耐压强度52MPa；900℃恒温氧化6h后，表面无气孔，质量几乎没有变化，抗氧化性极其出色。

Claims (7)

1.一种致密高抗氧化性氮化锆-赛隆复合陶瓷的制备方法，其特征在于以下步骤:
(1)将经过破碎处理的粉煤灰、碳粉、锆英石按质量分数20％～50％、20％～50％、10％～30％配料，以无水乙醇做球磨介质，经5～15h充分球磨混匀；
(2)将球磨混匀的配料在10～30MPa下压制成型，接着在70～120℃温度下干燥10～20h；随后将试样放入通有气氛的高温炉，在1300～1600℃保温2～10h合成氮化锆-赛隆复合粉体；
(3)将氮化锆-赛隆复合粉体磨碎，加入3％～5％粘结剂，以无水乙醇做球磨介质，经5～15h充分球磨混匀；
(4)将球磨混匀的配料在100～300MPa下压制成型，接着在70～120℃温度下干燥10～20h；随后将试样放入通有气氛的高温炉，在1400～1600℃保温5～10h得到氮化锆-赛隆复合陶瓷。
2.如权利要求1所述的制备方法，其特征还在于，所述的粉煤灰和锆英石为粒度≤45μm。
3.如权利要求1或2所述的制备方法，其特征还在于，所述的碳粉包括活性炭、炭黑、焦炭、煤粉中的一种。
4.如权利要求3所述的制备方法，其特征还在于，所述的球磨设备为行星球磨机，转速设定在300～500r·min-1，单向运行，每运行5h停歇1h。
5.如权利要求1、2或4所述的制备方法，其特征还在于，所述的压制方式为模压成型或等静压成型，保压时间为5min。
6.如权利要求5所述的制备方法，其特征还在于，所述的气氛为氮气，流量控制在1～3L·min-1。
7.如权利要求1、2、4或6所述的制备方法，其特征还在于，所述的高温炉为箱式电阻炉、管式电阻炉、隧道窑中的一种，升温速率设定为：以8℃·min-1的速率从室温升温至1000℃，接着以5℃·min-1的速率升温至1000～1300℃，再按3℃·min-1的速率升温至目标温度。
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* Cited by examiner, † Cited by third party
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JPH01301565A (ja) * 1988-05-30 1989-12-05 Agency Of Ind Science & Technol 高強度高耐酸化性サイアロン焼結体
CN101560099A (zh) * 2009-05-27 2009-10-21 东北大学 ZrN-Sialon-SiC复合粉体的制备方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
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